Copper-containing trisazo dyestuffs



schaft, Leverkusen, Germany,

COPPER-CONTAININGTRISAZODYESTUFFS Walther B enade and Hermann Goebel,Leverkusen, Geras cl, 260-147) The present invention relates tocopper-containing trisazo "dyestuifs and to a process for theirmanufacture;

more particularly it relates to copper complexes of poly-:aaodyestuifscorresponding to the formula In this formula X means ahydrogen atomor a sulfonic acid group and R stands for, a radical of anaminohydroxy naphthalene-mono or disulfonic acid coupled in o-positionto the hydroxyl group. l

. In accordance with the: invention it has been found at valuablecoppervcontaining trisazo dyesjtufls maybe obtained by i combiningdiazotized" ,1'-aminobenzene-2- carboxylicpacid or its, sulfonic acidderivatives, with I-(4'E aminophenyl)+3-methyl 5-pyrazolone or itssulfdnic acid derivatives, further diazotizing the l monoazo dyestuifsvnied States Patent 5; formed is salted thus=obtained,:and coupling themwith l-amino-Z-ethoxyfibres in green to olive shades which and,l5 parts,by'weight of L phenyD- -me th yl-5-pyrazolone;

.tion is completed, 26.7 parts by naphthalene or its sulfonic acidderivatives, diazotizing again the amino-disazo-dyestutfs thus obtained,and finally coupling them with an amino-hydroxynaphthalene monoordisulfonic acid in o-position to the hydroxyl group, and treating theresulting trisazo dyestuffs with copper-yielding agents.

The copper-containing trisazo dyestuffs obtainable according to theprocess of the invention dye vegetable distinguish themselves by .a verygood fastness to light.

The following examples are, given for the purpose of illustratin theinvention without, however, limiting it thereto. l l

Example] 21.? parts by weight of 2-amino-5-sulfbbenzoic acid arediazotized with 6.9 parts by weight of sodium nitrite percenthydrochloric acid, and coupled with 18 .9 parts byweight of 1-(4'-amino-The monoazo dyestutf is dissolved with 8 parts by weight of sodiumhydroxide, 6.9 parts by weight of sodium nitrite are added thereto, andthe mixture is run into parts by weight of a 35 percent hydrochloricacid and ice. After the diazotizaweight ofl-amino-2-ethoxynaphthalene-6-sulfonic acid and 10 parts by weight ofsodium acetate are added. The disazo out and isolated with the additionof 20 parts by weight of sodium carbonate at 30 C. The disazo dyestuir'thus obtained is further diazotized with 6.9 parts by weight of sodiumnitrite and parts by weight of 35 percent hydrochloric acid; the diazosalt solution is run into an aqueous solution of 31.5 parts by weight ofZ-phenylamino-S-hydroxynaphthalene-7-sulfonic acid in 420 parts byweight of pyridine and 50 parts by weight of aqueous ammonia. Thetrisaz-o dye stuif obtained corresponds in its free acid state to theformula:

note-G n grams ofsodium sulfate, there are introduced at 50 G. 100 gramsof a cotton fabric; the bath is heated to 90 C. and kept at thistemperature for 1 hour. The cotton fabric is then rinsed with water anddried. Clear green shades of very good fastness to light are obtained.

If in the preparation of the dyestufi described in this exampleZ-phenylamino--hydroxynaphthalene-7-sulfonic acid is replaced by theequivalent amount of2-(3'-carboxyphenylamino)-5-hydroxynaphthalene-7-sulfonic acid or2-(3'-sulfophenylamino) -5-hydroxynaphthalene-7-sulfonic acid, similardyestulfs are. obtained. Instead of.2-

"aimino-S-sulfobenzoic acid, 2-amino- 4-sulfob'enzoic .acid

may also be used as the starting component.

, 'Exa'mpll p 13.7 parts by weight of 'Z-aminobenzoic acid arediazotired with 6.9 parts by weight of sodium nitriteand parts by'weight of 35 percent hydrochloric acid and combined with 18.9 parts byweight of 1-'(4 "-aminophenyl')-3 methyl-5-pyrazolone. After theaddition; of 15 parts by weight of 35 percent hydrochloriclacidthe'monoaz'o dyestufi isfurther diazotized. The diazonium compound 'of themonoazo dyestuff is isolated stirred again and coupled with 6.9 parts byweight of 1-arnino-2- ethoxynaphthalene-6-sulfonic acid ,in the presenceof sodium acetate. The'paste of the isolated disazo dyestuff is stirredagain, further diazotized with 6.9 parts by weight of sodium nitriteafter the addition of 45 parts by weight of 35 percent hydrochloric acidand the diazonium compound of the disazo dyestutf thus formedis'combinedtreated with 50 parts by weight of copper sulfate and s parts by weightof sodium acetate, and converted parts by weight of sodium nitrite andinto the copper complex compound by boiling for several hours.

The copper-containing dyestuif thus obtained dyes cotton in oliveshades.

Example 3 13.7 parts by weight of Z-aminobenzoic acid are diazotizedwith 6.9 parts by weight of sodium nitrite and 15 parts by weight of 35percent hydrochloric acid, and coupled with 26.9 parts by. weight of1-(4'-amino-3'- su1fophenyl)-3-methy1-S-pyrazo1one. The monoazodyestufi' thus formed is isolated, further dia'zbtized 'v'vitfi 5.9parts by weight of hyd'ro'chloric acid; and c'ombined-witli 26:7 partsby weight of 1aminoeethexynapmhnens-6suironie acid. After stirring, thedisazo dyestufi formed is salted out after addition of sodiumcarb'onateat- 70"C., isolated and the paste is stirred again.' The disazodyestulr' is further diazotized. with parts byweight of 35 percenthydrochloric acid and 6.9 parts by weight of sodium nitrite, and thediazo compound is" run' into an aqueous solution of 35.9 parts by weighto f 2-( 3'-carboxyphenylamino) 5-hydroxynaphthalene-7-sulfonic acid, 420parts by weight of pyridine and parts by' wei'ghtof 2 0.percent BIO-COCaHs HO scan The'paste of thetrisazo dyestuff i s.dissolved in water,

0mm no N=N N=N no. I

it is converted into the copper complex compound as described in Example1.

The copper-containing dyestufi dyes cotton in green shades.

Example 4 21.7 parts by weight of Z-amino-S-sulfobenzoic acid arediazotized with 6.9 parts by weight of sodium nitrite and 15 parts byweight of 35 percent hydrochloric acid, and combined with 18.9 parts byweight of 1-(4-aminophenyl)-3-methyl-5-pyrazolone. The amino monazodyestufi thus obtained is further diazotized with 6.9 parts by weight ofsodium nitrite and 40 parts by weight of 35 percent hydrochloric acidand the diazonium compound is coupled with 18.7 parts by weight of1-amino-2-ethoxynaphthalene in the presence of sodium acetate. Afterstirring, the disazo dyestuff is salted out and isolated. The; paste ofthe fdisa'zo dyestu'tf is" stirred, further diazotized with 6.9 parts byweight of sodiuni-nitrite and 40 partsby: weight of 35 percenthydrochloric acid} and the diazoniumcompound is run-intoanaqueoussemtion of 3-1 .9- parts by-Weight of1'-aniino-8-hydroxy'naphthalene- 2,4-disulfonic-acid, 42O parts byweight-of 'pyridine and 50,. parts by weight of-ZOperce'nt aqueousammonisa v 6 The trisazo dyestuif thus formed coi iie s ponds in itsfree en emiuqhydroxyuaphthaleue sulfonlc acid bearing 881d state to theformula: :mmwepbmonm theizdhiidfih no 8 1-r==1-rE- g-om HO- 1 (Loon N001m HO Nu,

N==N N= it is converted into the copper complex compoufid by ffi lheeopper complex of the trisazo dyestuif corre- 2 boiling for severalhours WltljljgSO par tst by weght of sponjdmgmto thei formulaz $1! on Icopper sulfate and parts by weight of sodium acetate. 3. The coppercomplex of the trisazo dyestufi corre- The copper-containing dyestufisthus obtained dye 40 sponding to the formula cotton in yellowish oliveshades.

We claim: 1. Copper complexes of trisazo dyestuffs corresponding to theformula N=N-c--c-CH; HO-

N=NG--OGH| coon on no NH. x

on N=N Rs)! 0.3

no N=N N=Nl i PM 1: v wherein X stands for a member selected from thegroup 4. The copper complex of the trisazo dycstufi correconsisting of Hand -S0 H, and R means a radical of sponding to the formula N=NG-C-CH|OOH Hols on: no

N==N N=N HQ no i r v References Cited file of this patent UNITED STATES.PATENTS 2,342,451 Carson Feb. 22, 1944

1. COPPER COMPLEXES OF TRISAZO DYESTUFF CORRESPONDING TO THE FORMULA